Production of colored photographic images



United States Patent 3,008,827 PRODUCTION OF COLORED PHOTOGRAPHIC IMAGES Jan Jaeken, Hove-Antwerp, Belgium, assignor to Gevaert Photo-Producten N.V., Mortsel, Belgium, a Belgian company No Drawing. Filed June 18, 1958, Ser. No. 742,756 Claims priority, application Germany June 19, 1957 5 Claims. (Cl. 96-55) The present invention relates to a process for the. production of colored photographic images by color development in the presence of a color coupler, to photographic material containing a color coupler, and to photographic images produced according to this process.

It is known to produce a colored photographic image by developing a reducible silver salt image formed in a silver halide emulsion layer, with an aromatic amino developing agent in the presence of a color coupler, i.e. a compound which during developing couples with the oxidation product of the developing agent, to form a dyestuff.

It is further known to incorporate the color couplers in the light-sensitive emulsion layer, or in an adjacent layer thereto, of a photographic material. In order to prevent wandering of these couplers out of the layer wherein they initially were incorporated, the color coupler may be provided with a molecule enlarging group. Yellow colored images are :usually obtained by development in the presence of color couplers containing a methylene group free to react with an aromatic amino silver halide developing agent, more particularly in the presence of compounds containing an acylacetarnide group. In this way, it has been proposed to use color couplers of the formula wherein Y represents a heterocyolic nucleus.

The practical value of these couplers, however, is rather low, since the color density of the colored images obtained from these couplers is not sufficiently high, but the substitution of an aryl or a higher alkyl group for the methyl group does not eliminate this deficiency.

It is therefore an object of the present invention toprovide a light-sensitive photographic material for forming colored images having incorporated in a colloid layer of this material a non-diffusing color coupler forming a dye image of increased color density. It is a further object of this invention to provide a photographic silver halide emulsion containing such coupler. A still further object is to provide a method of producing colored images from such color couplers. Still further objects will appear from the following description and examples.

These objects are accomplished by using a benzoyl acetamide color coupler, the benzoyl group of which contains an alkoxy substituent containing a group rendering the color coupler fast to diffusion, and the amino group of which contains a heterocyclic nucleus as substituent.

Since it is known that the dyestuffs formed from benzoyl acetanilide couplers containing an alkoxy group on the benzoyl group are hypsochromic as distinguished from the dyestuffs formed from the couplers without alkoxy substituent, and therefore cannot be used for the manufacture of a positive material, it was to be expected that the alkoxy-substituted couplers of the present invention also should produce hypsochromic dyestuifs on color development.

Surprisingly it has now been found, however, that the dyestuffs obtained on color development from the couplers according to the present invention are bathochromic and thus differ from the dyestuffs obtained from the corresponding acetarylide coupler not containing an alkoxy phenyl group. It has further been found that the dye;

3,008,827 Patented Nov. 14,1961

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stuffs image obtained from the coupler, according to the invention are very intensive.

In consequence of the outstanding properties of the color couplers of the present invention, and of the particularly valuable results which are attained when using them, especially in the manufacture of a positive material, they are substantially different from those known in the art.

The color couplers which have been found to be especially suitable for accomplishing the objects of the present invention are compounds having the formula wherein R represents an alkyl group containing a linear chain comprising at least ten carbon atoms and preferably not more than twenty carbon atoms such as a dodecyl group, a hexadecyl group or an octadecyl group or a substituted alkyl group, the substituent containing at least eight carbon atoms, such as p-isooctyl-phenoxy-ethyl group, and Y represents a heterocyclic radical selected from those of the thiophene series e.g. a S-carbethoxythiophenyl-(2)-radical, those of the furane series, e.g. a S-carbethoxy-furyl radical, those of the thiazole series, e.g. a 4-methyl-thiazolyl-(2)-, a 4-phenyl-thiazolyl-(2)-, a 4-furyl-thiazolyl-(2)-, a 4-methyl-5-carboXyethyl-thiazolyl-(2)-, a 4,5-diphenyl-thiazolyl-(2)-, a 4-carboxymethyl-thiazoly1-(2)-, a 4-mor p-acylaminophenyl-thiazolyl- (2)-, a 4,S-dicarbethoxy-thiazolyl-(2-)-, a 4methyl-5-car-' benzimidazyl-(2)-radical, those of the pyridine series, e.g.

a. 5-acylazmino-pyridyl-(2)-, a pyridyl-(4)- or a chinolyl- (2)-radical, those of the 1,3- or 1,4-diazine series, e.g. a 2,6-dihydroxy-4-methyl-pyrimidyl-(5)-radical, those of the 1,3,4thiadiazole series, e.g. a 5-carbomethoxyethyl-- 1,3,4-thiadiazolyl-(2)-radical, those of the 1,3,4-oxodiazole series, those of the 1,2,4-triazole series, e.g. a 1-(pcarbethoxyphenyl)-3-amino-triazolyl-(5)- or a l-(p-carbethoxy-phenyl)-triaxolyl-(5)-radical and those of the 1,3,5-triazine series.

In these compounds the methylene group attached to the two carbonyl groups is reactive with aromatic amino developing agents in the development process. One or both of the hydrogen atoms of the methylene group may, in general, be substituted by certain groups without destroying the chemical activity of the methylene group. It is necessary, however, that the substituents are groups capable of splitting off either before development occurs, for instance by the action of the alkali in the developing solution, or during the color development.

It will be noted that the color couplers according to the present invention possess a central p-oxybenzoyl acetamide part conferring a coupler function to which is attached through the acid amide linkage a heterocyclic nucleus Y which preferably contains a group conferring solubility to the coupler, and to'which is attached through the ether linkage an alkyl group or a substituted alkyl group which serves to prevent wandering of the coupler the new color couplers are incorporated into a colloid 3 layer of a light-sensitive photographic element; preferably they are incorporated into the silver halide emulsion layer but in some cases useful results can be attained when the coupler is incorporated in a layer adjacent to the silver halide emulsion layer or separated therefrom by a water-permeable colloid layer.

The aromatic amino compounds which in the present invention are used as developing agent for the silver halide comprise monodi-, and tri-amino aryl compounds, particularly N,N-dia-lkylparaphenylene diamincs, and their derivatives such as N,N-dialkyl-N-sulphomethyl-pphenylene diamine, and N,N-dialkyl-N'-carboxymethyl p-phenylene di-amines. As mono-amino developing agents are considered compounds such as aminophenols, aminocresols, aminonaphthols and halogen derivatives of these compounds.

The couplers of the invention may be employed for the production of colored photographic images in layers of gelatin or other carriers for the silver halide such as collodium, cellulose organic acid esters or synthetic resins such as pclyvinylalcohol. The support for the emulsion may be a transparent material such as glass, cellulose ester or a synthetic film forming resin such as polystyrene or polyester, or a non-transparent reflecting material such as paper or an opaque cellulose ester layer. The emulsion containing the couplers of the present invention may be coated as a single layer on a support or as a layer of a photographic material containing 'a plurality of emulsion layers coated on one or both sides of the support. The emulsion layers of the multilayer material may be differentially sensitized for the formation of a natural color image in the well known manner.

The couplers of the present invention advantageously may be incorporated into the blue sensitive emulsion layer of a multi-layer color film of the positive type such as e.g. the cine film Gevacolor Positive Type 952, the general properties of which together with a method for the production of color prints on this film and a method for processing the exposed film are described in the booklet Motion Picture Films for Professional Use, issued June 1957 by Gevaert Photo-Producten N.V., Mortsel Antwerp, Belgium, pages 60-64 and 77-84.

The following examples illustrate the present invention without limiting, however, in any way the scope thereof. Example 1 32.3 g. of 4-{fi-[4-(1,1,3,3-tetramethylbutyl)-phenoxy]- ethoxy}-benzoyl acetic methyl ester (prepared according to British specification 774,421) and 18.3 g. of Z-amino- 4,5-dicarbethoxythiaZ/ole (prepared according to L. Conover, I. Am. Chem. Soc. 72 (1950), 5221/25) dissolved in 800 can. of xylene are refluxed for 3 h. The methanol formed is distilled oil with part of the xylene whereby the level of the reacting liquid is kept at the same height by addition of fresh xylene. On cooling, the amide crystallizes out. After recrystallization from n-butanol a product is obtained corresponding to the following formula:

Melting point: 181 C.

A solution of 4 g. of this color coupler is added to 1 kg. of a photographic silver halide emulsion. After coating this emulsion onto a layer support, exposing and developing, a yellow image is obtained with an absorption maximum at 460 m Example 2 The 2-amino-4,5-dicarbethoxythiazole used in the 0 synthesis of the coupler of Example 1 is replaced by a 7 product corresponding to the following formula:

SCGHr-C O O C2Ht HzN- C 4 (prepared according to Conrad, Ann. 285 (1895), 208) and the n-butanol used for recrystallization by acetonitrile. A color coupler is obtained yielding after color development a yellow image with an absorption maximum at 450 m Mel-ting point: 178 C.

Example 3 The 2-amino-4,S-dicarbethoxythiazole used in the synthesis of the coupler of Example 1 is replaced by a product corresponding to the following formula:

(prepared according to Dodson, J. Am. Chem. Soc. 67 (1945), 2242) and the n-butanol used for recrystallization by ethanol. A color coupler is obtained yielding after color development a yellow image with an absorption maximum at 460 mp. Melting point: 181 C.

Example 4 The 2-arnino-4,S-dicarbethoxythiazole used in the synthesis of the coupler of Example 1 is replaced by a product corresponding to the following formula:

(prepared according to Erlenmeyer, Helv. Chim. Acta 27 (1944), 1432, or Dann, Ber. 76 (1943), 419) and the n butanol used for the recrystallization by acetic acid. A color coupler is obtained yielding after color development a yellow image with an absorption maximum at 460 m Melting point: 195 C.

Example 5 910 g. of keto ester according to Example 1, and 262 g. of 2-amino-5-nitropyridine (prepared according to Plazek, Ber. 61 (1928), 1815) dissolved in 3 lit. of toluene and 3 lit. of xylene are refluxed for 24 h. in such a way that part of the toluene can distill oil with the methanol formed. On cooling the reaction mixture, 21 compound crystallizes out which after recrystallization from acetonitrile melts at 143 C.

140 g. of this compound are reduced in the presence of g. of iron powder in a boiling mixture of 625 cm. of acetonitrile, 625 cm. of glacial acetic acid and 1125 cm. of water. After sucking off the iron which has not reacted, the filtrate is poured into a mixture of 1250 g. of ice and 1250 cm. of concentrated hydrochloric acid. The precipitate obtained is sucked off, Washed with an aqueous 2.5 N hydrochloric acid solution until no iron is present any longer and then dissolved in chloroform. The solution is Washed with an aqueous sodium carbonate solution until free of acid, filtered through a dry sodium sulphate layer and evaporated to dryness. The residue is washed with ether and after recrystallization from benzene an amine is obtained. Melting point: 137 C.

89 g. of the amine are dissolved in 1 liter of boiling benzene. After adding 37 g. of maleic anhydride dissolved in 270 cm. of benzene, the mixture is refluxed for /2 11., cooled off, sucked off and washed with ether.

.'. -LAR.

A color coupler is obtained corresponding to the following formula:

colloid layers coated thereon, at least one of said colloid layers being a light-sensitive silver halide emulsion layer,

Melting point: 190 C. (decomposition). After recrystallization from benzene, the melting point remains unchanged.

A solution of 4 g. of this color coupler is added to 1 kg. of a photographic silver halide emulsion. After coating this emulsion onto a layer support, exposing and developing, a yellow image is obtained with an absorption maximum at 445 mu.

Example 6 8.6 g. of 2-amino-5-carbethoxythiazole and 25 g. of p-cetyl-oxybenzoyl acetic ethyl ester (prepared according to British patent application 23,2'67/ 56) are refluxed for 6 h., dissolved in 200 cm. of xylene. After cooling the precipitate is sucked ofit' and washed with benzene. A color coupler is obtained with a melting point of 150 C. By recrystallization from methylcellosolve, the melting point is not increased.

The color coupler corresponds to the following formula:

S-C-C O O 02H,

A solution of 4 g. of this color coupler is added to 1 kg. of a photographic silver halide emulsion. After coating this emulsion onto a layer support, exposing and developing, a yellow image is obtained with an absorption maximum at 455 mg.

I claim:

1. A light-sensitive photographic material for forming a colored image, comprising a support, a plurality of colloid layers coated thereon, at least one of said colloid layers being a light-sensitive silver halide emulsion layer, and a color coupler incorporated in one of the colloid layers, the color coupler containing a methylene group free to react with an aromatic amino silver halide de veloping agent to form a dye, and having the formula wherein R represents a member selected from the group consisting of an alkyl radical and a substituted alkyl radical, said alkyl radical consisting of a linear chain of at least ten carbon atoms and more than twenty carbon atoms, said substituted alkyl radical being a p-isooctylphenoxy ethyl radical, and Y represents a substituted thiazolyl radical selected from the group consisting of a 4-methyl-thiazolyl-(2)-radical, a 4-phenyl-thiazolyl- (2)-radical, a 4-furyl-thiazolyl-(2)-radical, a 4-methyl- S-carbethoxy ethyl-thiazolyl-(2)-radical, a 4,5-diphenylthiazoly1-(2)-radical, a 4-carboxymethyl-thiazolyl-(2)- radical, a 4-rn-acylaminophenyl-thiazolyl-(2)-radical, a 4 p acylaminophenyl thiazolyl (2) radical, a 4,5-dicarbethoxy-thiazolyl-(2)-radical, a 4-methyl-5-carbethoxy-methyl-thiazolyl-(2)-radical, a 4-methyl-5-carbethoxy-thiazolyl-(2)-radical, a 5-carboxy-thiazolyl-(2)- radical, a S-carbomethoxy-thiazolyl-(2)-radical, a S-carbethoxy-thiazolyl-(Z)-radical, and a S-carbethoxy-thiazolyl-( 2) -radical.

2. A light-sensitive photographic material for forming a colored image, comprising a support, a plurality of and a color coupler incorporated in one of the colloid layers, the color coupler containing a methylene group free to react with an aromatic amino silver halide developing agent to form a dye, and having the formula wherein R represents a member selected from the group consisting of an alkyl radical and a substituted alkyl radical, said alkyl radical consisting of a linear chain of at least ten carbon atoms and not more than twenty carbon atoms, said substituted alkyl radical being a p-isooctylphenoxy ethyl radical, and Y represents a radical of the pyridine series selected from the group consisting of a S-acylamino-pyridyMZ)-radical, a pyridy1-(4)-radical, and a quinolyl-(2) -radical.

3. In the method of producing a colored photographic image, the steps of treating, in the presence of a color coupler, a photographic material containing a silver halide emulsion layer wherein a reducible silver salt image has been formed with a developer containing an aromatic amino silver halide developing agent, said color coupler containing a methylene group free to react with an arcmatic amino silver halide developing agent to form a dye, and having the formula 11-0-00 0-0112-0 O-NHY wherein R represents a member selected from the group consisting of an alkyl radical and a substituted alkyl radical, said alkyl radical consisting of a linear chain of at least ten carbon atoms and not more than twenty carbon atoms, said substituted alkyl radical being a p-isooctylphenoxy ethyl radical, and Y represents a heterocyclic radical selected from the group consisting of a 4-methyl-thiazolyl-(2)-radica1, a 4-phenyl-thiazolyl-(2)- radical, a 4-furyl-thiazoly1-(2)-radical, a 4methyl-5- carbethoxy ethyl-thiazolyl-(2)-radical, a 4,5-diphenylthiazolyl-(2)-radical, a 4-carboxymethyl-thiazolyl-(2) radical, a 4-m-acylaminophenyl-thiazolyl-(2)-radical, a 4-p-acylaminophenyl-thiazolyl-(2)-radical, a 4,5-dicarbethoxy-thiazolyl(2)-radical, a 4-methyl-5-carbethoxymethyl-thiazolyl-(2)-radical, a 4-methyl-5-carbethoxythiazolyl-(2)-radical, a S-carboxy-thiazolyl-(Z)-radical, a S-carbomethoxy-thiazolyl-(2)-radical, a S-carbethoxythiazolyl-(2)-radical, a S-carbethoxy-thiazolyl-(2)-radical, a S acylamino-pyridyl-(Z)-radical, a pyn'dyl-(4)-radical and a quinolyl-(2)-radical.

4. The light-sensitive photographic material according to claim 2, the light-sensitive silver halide emulsion layer having said color coupler incorporated therein.

5. The light-sensitive photographic material according to claim 1, the light-sensitive silver halide emulsion layer having said color coupler incorporated therein.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A LIGHT-SENSITIVE PHOTOGRAPHIC MATERIAL FOR FORMING A COLORED IMAGE, COMPRISING A SUPPORT, A PLURALITY OF COLLOID LAYERS COATED THEREON, AT LEAST ONE OF SAID COLLOID LAYERS BEING A LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER, AND A COLOR COUPLER INCORPORATED IN ONE OF THE COLLOID LAYERS, THE COLOR COUPLER CONTAINING A METHYLENE GROUP FREE TO REACT WITH AN AROMATIC AMINO SILVER HALIDE DEVELOPING AGENT TO FORM A DYE, AND HAVING THE FORMULA 